1. Field of the Invention
This invention relates to multi-stage acrylic polymeric compositions, to a process of producing films and sheets by calendering the multi-stage acrylic polymeric compositions, to composites of coated textile materials and other substrates wherein the coating is a film or sheet of the calendered multi-stage acrylic polymer composition, and to a process of treating a textile material or other substrate with sheets of films of the calendered multi-stage acrylic polymeric compositions. The use of the compositions according to the invention provides improvement of various properties of textile materials treated therewith, such as flexibility and a leather-like hand while retaining good low-temperature properties.
2. Prior Art And Related Applications
The use of calenders for processing synthetic thermoplastic materials to produce films or sheets is well-known. The state of the art of calendering synthetic thermoplastic materials is described in the following: "Calendering," Eberhart Meinicke, pages 802-819 in Herman F. Mark, Norman G. Gaylord, and Norman M. Bikales, eds., Encyclopedia of Polymer Science and Technology, Volume 2, Interscience Division, John Wiley & Sons, New York, 1965; "Calendering," G. W. Eighmy, Jr., pages 237-238 in Modern Plastics Encyclopedia, 1978-1979; "Calendering Today Isn't Just Vinyls," pages 61-63 in Modern Plastics, June 1974; and "Calendering," G. W. Eighmy, page 451 in Modern Plastics Encyclopedia, 1970-1971.
The bulk of thermoplastic materials processed on calenders is poly(vinyl chloride), sometimes referred to hereafter as PVC. Other thermoplastic materials more recently used in calendering operations include acrylonitrile-butadiene-styrene polymer-modified PVC and polyethylene-modified PVC, cellulose acetate, polyolefins including polyethylene, chlorinated polyethylene and polypropylene, and polyurethane elastomers. Interest in the use of non-PVC synthetic thermoplastic materials has been increasing due to environmental and ecological considerations which favor decreasing the use of PVC and of plasticizers normally used with PVC. Although many synthetic thermoplastic materials have been used heretofore in place of PVC in calendering operations, the use of soft and flexible acrylic polymeric materials as the predominant thermoplastic material is not known for the production of films and sheets by calendering, the films and sheets thereby produced being useful for coating fabrics and textiles or other substrates to produce composites having applications such as home furniture upholstery, automotive upholstery, clothing fabric, luggage, wall covering, and the like.
Applicant's copending application, U.S. Ser. No. 945,733, filed Sept. 25, 1978, discloses a textile treating composition and an article comprising a textile material treated therewith, wherein the textile treating composition comprises an acrylic latex, the particles of which comprise about 30-60% by weight of polymeric core and about 70-40% by weight of a polymeric shell, wherein said core is formed by emulsion polymerization of a first monomer composition consisting essentially of:
70-95% by weight of C.sub.1 -C.sub.8 alkyl acrylate, PA1 0-15% by weight of a C.sub.1 -C.sub.8 alkyl methacrylate, PA1 4-10% by weight of acrylamide or methacrylamide, PA1 0-0.3% by weight of allyl methacrylate, and PA1 0-2% by weight of itaconic acid; PA1 40-70% by weight of a C.sub.1 -C.sub.8 alkyl acrylate, PA1 20-50% by weight of a C.sub.1 -C.sub.8 alkyl methacrylate, PA1 2-10% by weight of N-methylolacrylamide, N-methylol methacrylamide, or a mixture of methacrylamide and N-methylolacrylamide, PA1 and 0-2% by weight of itaconic acid. PA1 (i) about 0.5% to 6% by weight on the total first monomer composition of a graftlinking monomer or an active crosslinking monomer, and PA1 (ii) about 4% to 10% by weight on the total first monomer composition of a latent crosslinking monomer; and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of: PA1 (a) about 70-95% by weight of at least one (C.sub.1 -C.sub.8) alkyl acrylate, PA1 (b) about 0-15% by weight of at least one (C.sub.1 -C.sub.8) alkyl methacrylate, PA1 (c) about 4-10% by weight of a latent cross-linking monomer selected from acrylamide or methacrylamide, and PA1 (d) about 0.5-4% by weight of at least one alpha, beta-ethylenically unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, and itaconic acid; PA1 (a) about 40-70% by weight of at least one (C.sub.1 -C.sub.8) alkyl acrylate, PA1 (b) about 20-50% by weight of at least one (C.sub.1 -C.sub.8) alkyl methacrylate, PA1 (c) about 4-10% by weight of a latent crosslinking monomer selected from acrylamide and methacrylamide, and PA1 (d) about 0.5-4% by weight of at least one alpha, beta-ethylenically unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, and itaconic acid; and PA1 (a) about 50-100% by weight of methyl methacrylate, and PA1 (b) about 0-50% by weight of a comonomer selected from those comonomers copolymerizable with methyl methacrylate and having a calculated T.sub.g of less than 0.degree. C.
and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
Commonly assigned U.S. Pat. No. 4,107,120 and U.S. Pat. No. 4,181,769 to Plamondon, the later being a division of the former (U.S. Pat. No. 4,107,120), disclose a textile treating composition and an article comprising a textile material treated therewith, wherein the textile treating composition consists essentially of an acrylic latex, the particles of which comprise about 30-60% by weight of a polymeric core and about 70-40% by weight of a polymeric shell, wherein the core is formed by emulsion polymerization of a first monomer composition consisting of:
(a) a major amount of a principal monomer system, and PA0 (b) a minor amount of a crosslinking monomer system comprising: PA0 (a) a major amount of a principal monomer system; and PA0 (b) about 2% to 10% on the total second monomer composition of a latent crosslinking monomer; the monomers of said first monomer composition being selected to provide a T.sub.g in said core of -20.degree. C. or lower, and the monomers of said second monomer composition being selected to provide a T.sub.g in said shell of about 60.degree. C. to about -10.degree. C. PA0 (1) said first stage is formed by emulsion polymerization of a first monomer composition having a T.sub.g of about (-) 10.degree. C. or lower consisting essentially of: PA0 (2) said second stage is formed by emulsion polymerization, in the presence of said first stage, of a second monomer composition having a T.sub.g of about (-) 10.degree. to (+) 60.degree. C. consisting essentially of: PA0 (3) said third stage is formed by emulsion polymerization, in the presence of said second stage polymerization product, of a third monomer composition consisting essentially of:
Carty, U.S. Pat. No. 4,086,296, discloses a blend of a thermoplastic polymer (e.g. ABS resins, polystyrene, polypropylene, polyesters such as polyethylene terephthalate, polyamides such as poly[caprolactam] and polyurethanes which are mentioned in column 6, lines 23 to 60) with a multiphase acrylic composite polymer, the latter functioning as a lubricant and/or processing aid in the above-mentioned thermoplastic polymers.
Lane et al, U.S. Pat. No. 3,745,196, disclose a polystage elastomer having a first stage polymer having a glass temperature below about -35.degree. C. comprising at least 50% by weight of an alkyl acrylate and, optionally, 0 to 5% by weight of a polyethylenically unsaturated crosslinking comonomer, 0 to 10% by weight of a curing site-containing monomer, and from 0 to 50% by weight of at least one monomer selected from alkoxyalkyl acrylates, alkylthioalkyl acrylates, cyanoalkoxyalkyl acrylates, and nitrile substituted alkyl acrylates. The final stage of the elastomer comprises at least 60% by weight of ethyl acrylate and/or methyl acrylate and, optionally, 0 to 40% by weight of comonomers such as acrylonitrile, lower (C.sub.1 -C.sub.4) alkyl esters of acrylic acid and curing--site monomers.
Griffin, U.S. Pat. No. 3,458,603 discloses a three-stage granular polymerization process for the production of thermoplastic polymer materials suitable for injection molding to manufacture various molded articles.
Dickie, U.S. Pat. No. 3,787,522, discloses a particulate thermoplastic material having at least two stages formed by emulsion polymerization and having a rubber-like core of a major amount of an alkyl acrylate and a minor amount of a polyethylenically unsaturated compound as a crosslinking agent and a glass-like outer shell of about 30 to 99 molar parts of methyl methacrylate and about 1 to 70 molar parts of monomers copolymerizable with methyl methacrylate. The polymers are useful as modifiers of thermoset polymers and as intermediates for forming other rubber-like and/or rubber-modified materials suitable for molding with each other and with other thermoplastic materials.
Myers, U.S. Pat. No. 3,971,835, discloses a three-stage, sequentially produced graft copolymer comprising a non-rubbery, hard first stage polymer of 50 to 100 weight percent of a vinyl aromatic compound, 0 to 50 weight % of a different monovinylidene monomer and 0 to 10 weight % of a polyfunctional crosslinking monomer; a second stage rubbery polymer of 50 to 100 weight % of butadiene, isoprene, chloroprene, and an alkyl acrylate or mixtures thereof wherein the alkyl group has about 3 to 8 carbon atoms, 0 to 50 weight % of a monovinylidene monomer and 0 to 10 weight % of a polyfunctional crosslinking agent; and a third stage polymer of 50 to 100 weight % of an alkyl methacrylate wherein the alkyl group has 1 to 4 carbon atoms, 0 to 50 weight % of a vinylidene monomer, and 0 to 10 weight % of a polyfunctional crosslinking monomer. The 3-stage graft polymer is used as a modifier for vinyl halide polymers.
Owens, U.S. Pat. No. 3,793,402 and 3,843,753, discloses broadly acrylic heteropolymers having two or more stages.
Although the polymer compositions mentioned above generally provide excellent properties when used as latex coatings on fabrics or as processing aids for handling other polymers such as poly(vinyl chloride), they possess deficiencies which do not permit their use as thermoplastic materials for calendering into films or sheets.